Residual fuels improved in its flow characteristics by a copolymer of c{11 {11 to c{11 {11 linear alpha-olefin and styrene or a c{11 {11 to c{11 {11 alpha-olefin

ABSTRACT

Hydrocarbon polymers comprising linear C18 alkyl side chains are added to residual fuels to improve their pour point and flow characteristics. These polymers are prepared by polymerizing C20C40 alpha-olefins in the presence of a Ziegler-type catalyst to a number average molecular weight within the range between about 500 and 125,000. Particularly effective polymers are prepared from C3-C18 alpha-olefins and C20-C40 alpha-olefins.

United States Patent 1191 Rossi et al.

11] 3,790,358 1 Feb. 5, 1974 RESIDUAL FUELS IMPROVED IN ITS FLOW CHARACTERISTICS BY A COPOLYMER 0F C22 TO C40 LINEAR ALPHA-OLEFIN AND STYRENE OR A C3 TQ V P -QLHEEINU. 1

Inventors: Albert Rossi, Jersey City; Norman Jacobson, East Brunswick; Harold N. Miller, Millington, all of NJ.

Esso Research and Engineering Company, Linden, NJ.

Filed: July 30, 1971 Appl. No.: 167,867

Related US. Application Data Continuation of Ser. No. 762,372, Sept. 16, 1968, abandoned.

Assignee:

US. Cl. 44/62, 44/80 Int. Cl Cl0l 1/16 Field of Search 44/62, 80; 252/59 References Cited UNITED STATES PATENTS 11/1964 De Vries et al 44/8O X 3,271,121 9/1966 Young et al. 44/62 FOREIGN PATENTS OR APPLICATIONS 6,603,483 9/1967 Netherlands 44/62 Primary ExaminerDaniel E. Wyman Assistant ExaminerW. J. Shine Attorney, Agent, or Firm-Pearlman and Stahl; Frank T. Johmann 1 6 Claims, No Drawings 3 ,790 ,3 5 8 1 2 RESIDUAL FUELS IMPROVED IN ITS FLOW which contains about 20 wt. percent wax. This wax in- CHARACTERISTICS BY A COPOLYMER OF C22 cludes waxes of relatively high molecular weight, e.g., TO C LINEAR ALPHA-OLEFIN AND STYRENE from about C and greater, which give rise to a number OR AC T C ALPHA-OLEFIN of the above-mentioned problems, i.e., the transport- MW W ing, storing, etc., of this kind of heavy oil.

This application is a continuation of our copending H w v r, while such Zelten residuum typifies the application 762,372, filed p 16, 1968, HOW kind of high-wax containing oils which exemplify undeabandoned sirable flow properties and the like, such residuum is,

in fact, a premium oil as compared to other crude re- BACKGROUND OF THE INVENTION 10 sidua which have much lower pour points. This fact 1. Field of the Invention may be illustrated by a comparison of Zelten waxy oil The present invention is concerned with residual with crude petroleum residue, known as Aramco Arid fuels having improved pour and flow characteristics. Kuwait, as illustrated in the following Table II.

More particularly, the invention relates to a residual fuel containing, as a wax crystal modifier, a polymer of TABLE II C-C40 alphaolefins- Heavy Fuel Oil Inspections I 2. Description of the Prior Art Zelten Ammo Kuwa" Target v01. 680FVT When petroleum oils are sufficiently cooled, there is In Crude 35 39 37 formed a crystalline precipitate of the wax present in Inspections on the oil. As the temperature is further lowered, the con- 20 223x11 22 l 5 l 4 centration of solid material increases, developing a gel Sulfur, iv, 0, 3, 4, m

.Viscosity, SF caused by the formation of a coherent three at 220R 7 65 I I0 340 M75 dimensional network of wax crystals. As a result of this MN], wt. 2'3 33 7 m crystal structure, large amounts of oil are entrained in go gadso q 4 5 8 9 lO-H 25 ar on,wt. o

the crystal lattice of the wax, thereby preventing its Flow s 105 65 55 75 max flow. The temperature which is 5 F. higher than that at Hot Filtration Sed., which oil ceases to flow when chilled under specified conditions is referred to as the pour point.

The pour points of petroleum oil vary widely, for The inspections shown in the foregoing Table II illusample, some oils solidify far below zero while others trate that the Zeheh residuum is a P i Product freeze at temperatures up to 80 or 120F. by virtue of per set as s a valuable Preduet for hlehdmg and their wax content alone. It is obvious, therefore, that for impmvmg e heavy fuel ohs e to its low sulfur the pour point is critical with regard to the flow characcement low Viscosity) 10w MNI (Modlfied Naphtha teristicsand, consequently, adversely affect the storsolubles), eh cohradsoh cmjboh humherage mixing pumping, of Such oil Thus, pour point therrnore, it is low in ash and vanad um content. These Characteristics are i ifi to the design and/01. v qualities also make Zelten crude residuum an excellent operation facilities for the storage, heat exchange, Cracking e for ohtainihg Various valueble Products, pumping, etc., of the oil. Naturally, an oil having a high Such as Stralght chem fi r and e AS p e flow point, e.g., light fuel oils having flow points above ehted, the eohhhh headed by the hotahoh e 20F. and residual fuels having flow points above about 40 dleates h par meters of blends which are desirable F. would provide a serious problem relative to the g e Zelten residuum as a hlehdmg stock -r d i f the f ili i mentioned above providing the flow point can be sultably lowered. For

Typical examples of petroleum oils which exemplify eXamPle, it y h desireble to mix the Zelten e the undesirable characteristic of having high pour or m a 50/50 mixture wlth the Arame-o Kuwait flow points are the residual oils set forth in the follow- 45 siduumwhile such blending lowers the x n e ing Table L the flow point is generally not s ufficiently reduced so TABLE I PEIROLEU M. RESDQALQIL-fi.

Location and field Libya Nigeria Venezuela Sumatra Sari I Zelten Mabruk Raguba Dahra Waha Bomu Ebubu Oloibiri Joaquin Minas Flow points of residual F.) 105 110 97 /100 85 100+ 100+ 100+ FVT cut point of residual* 680+ 680+ 650+ 650+ 650 650 650 650 650 0 A FVT Final vapor temperature. l While the present invention is directed to substanas to significantly change the characteristics of the retially all petroleum fuel oils containing components of sulting mixture. petroleum residual oils, special reference is made to Thus, it is found that blending of the extremely high high pour point fuels, e.g.. .residual' fuel oils boiling wax-containing petroleum residual oils with other above about 600F. and containing C -C paraffins. blending stocks maylower the wax content, the pour or Particular reference is made to the residuum ofa North flow point cannot be satisfactorily reduced without African crude identified above as Zelten residuum using further processing.

As mentioned above, because of the ability of high pour point, e.g., high wax content oils to resist the free flow at lower temperatures, their use at these conditions is very limited. Conventional dewaxing operations to reduce the pour point are not always feasible nor satisfactory, and they are usually expensive. For this reason, additives capable of lowering the pourpoint of these oils are required to extend their use at lower temperatures.

The use of additives to lower t h e pour point of mineral oils is well known. For example, a wide variety of compounds has been found to be effective as pour point depressants for middle distillates and lubricating oils. Among the best known are Paraflow, Santopour and Acryloid and their modifications. They are prepared either by condensing aromatic compounds with long chain paraffins, such as chlorinated wax, or by condensing olefinic esters. It is generally considered that thesepour depressants are effective in that in cooling an additive containing oil, the hydrocarbon chain of the additive becomes incorporated into the crystal lattice of the separated wax, while the other part of the pour depressant molecule prevents the crystals from adhering together to form a gel structure. Unfortunately, these well-known pour depressants are not effective in all petroleum base stocks, usually being effective in either middle distillates or lubricating oil fractions. However, none of these well-known pour depressants are effective in the residual fuels of the type with which this invention is concerned.

US. Pat. No. 3,248,186 discloses that the problems associated with the use of the residual fuels of the invention can be overcome by incorporating into the fuel a polyacylated polystyrene wherein the acyl group contains a long straight alkyl chain. This patent also discloses that additives of the type represented by waxnaphthalene condensates, C alkyl polystyrene, polyvinyl stearate, etc. are not effective in the residual oils of this invention. Further, this patent shows that n-C acyl polystyrene is effective in the residual fuel whereas n-C alkyl polystyrene is ineffective, suggesting that this difference in effectiveness is due to the type of side chain involved, i.e., acyl vs. alkyl, since the number of carbon atoms in the side chain is the same. Actually, the degree of effectiveness of a polymeric pour depressant appears to be somehow related to not only the type of side chain involved but also to the molecular weight of the polymer and the makeup of the polymer backbone and it cannot be predicted with certainty whether an untried class of polymers will improve the flow characteristics of a particular petroleum fraction. In accordance with this invention, it has been found that a new class of polymeric additives prepared from long chain alpha-olefins are very effective pour depressants and flow improvers for fuels containing residual oil components.

SUMMARY OF THE INVENTION Residual fuels having improved flow characteristics are prepared by incorporating into the fuel from about 0.001 to 2.0 wt. percent based upon fuel to be treated, preferably 0.01 to 1.0 wt. percent of an oil-soluble polymer comprising at least wt. percent of a Cary-C alpha-olefin, said polymer having a number average molecular weight in the range of about 500 to 125,000, preferably about 1000 to about 40,000 as measured by Vapor Phase Osmometry (VPO).

The C C,,, alpha-olefin monomer which is used to prepare the polymer of the invention may be represented by the following general formula: I-I,C CHR wherein R is a substantially linear aliphatic hydrocarbon radical containing from 18 to 38 carbon atoms. It is preferred, however, that R have the formula: CH (CH Cl-I wherein n is a whole number within the range between about 16 and 36, more preferably within the range between about 18 and 26. The term substantially linear is used herein to denote those aliphatic side chains, i.e., R, which contain no more than one lower alkyl side chain such as methyl, ethyl, etc., in the radical and whereinsaid lower alkyl side chain, when present in the radical, is located at a position such that R has a linear portion containing at least 18 carbon atoms. Examples of such monomers include, among others, n-eicosene-l, 3-methyl docosene-l, ndocosene-l, n-tetracosene-l, 3-methyl tetracosene-l, n-hexacosene-1, n-triacontene-l and the like.

Polymers prepared from the aforedescribed C C alpha-olefms when blended with fuels containing residual oils are effective for lowering the pourv point and improving the flowability thereof. It has unexpectedly been found, however, that the polymers having the greatest ability to improve the flow characteristics of fuels containing residual fuel oil components are prepared from the aforedescribed C C alpha-olefins and certain lower alpha-olefins. While not known with 'Of these, copolymers containing 4 to 50 wt. percent of a C -C alpha-olefin and 50 to 96 wt. percent of a linear C -C alpha-olefin are particularly effective. An especially preferred polymer comprises 20 to 40 wt. percent of a C -C alpha-olefin and 60-80 wt. percent of a C -C aplha-olefin. I The C C mono-ethyenially unstaturated monomers which are polymerized with the aforedescribed C -C alpha-olefins may be represented by the following general formula: H,C CHR' wherein R is a hydrocarbon radical containing from one to 16 carbon atoms. Since the lower monomer apparently serves only to disrupt the degree of order of the polymer, there appears to be-no criticality as to the configuration of R. Accordingly, R may be an alkyl, aralkyl, aryl, alkylaryl or cycloaliphatic group. Examples of such monomers include propylene, butene-l, hexene-l, octene-1, decene-l, 3-methyl decene-l, tetradecene-l, styrene and styrene derivatives such as p-methyl styrene, p-isopropyl styrene, alpha-methyl styrene, etc.

The aforedescribed C -C alpha-olefins may be polymerized with various other monomers. For example, effective copolymers comprise 20 to 100 wt. percent of a C -C alpha-olefin of the invention and 0 to wt. percent of a polymerizable C C diolefin. Similarly, the polymers of the invention may comprise 20 to wt. percent of the aforedescribed egg-C alpha-olefin, 0 to 80 wt. percent of the aforedescribed C C alpha-olefin and 0 to 80 wt. percent of a polymerizable C C diolefin. These diolefins which are useful for polymerization with the aforedescribed alpha-olefins include the bicyclic, alicyclic or aliphatic nonconjugated diolefins containing from about six to about 28 carbon atoms, preferablyfrom about six to 12 carbon atoms. Nonlimiting examples of suitable-monomers include 1,5 cyclooctadiene, methylene norbornene, dimethylene norbornene, l,5-hexadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 1,5-cyclodecadiene, 2,4-dimethyl-2,7-octadiene, 3(2-methyl-1-propenyl) cyclopentene, l,5-octadecadiene, and thelike.

The polymers of this invention may be conventionally prepared by polymerizing the monomers under relatively mild conditions of temperature and pressure in the presence of a Ziegler-type catalyst, i.e., a mixture of a compound derived from a Group IV, V or VI metal of the Periodic Table in combination with an organo metallic compound of a Group I, II, or III metal of the Periodic Table wherein the amount of the compound derived from a Group IV VI metal may range from 0.01 to 2.0 moles per mole of the organo metallic compound.

Effective catalysts for polymerizing the monomers of the invention include the following combinations: aluminum triisobutyl and vanadium trichloride; aluminum triisobutyl, aluminum chloride,.-and vanadium trichloride; vanadium tetrachloride and aluminum trihexyl; vanadium trichloride and aluminum trihexyl;'vanadium triacetylacetonate and aluminum diethyl chloride; titanium tetrachloride and aluminum trihexyl; vanadium trichloride and aluminum trihexyl; titanium trichloride and aluminum trihexyl; titanium dichloride and aluminum trihexyl; etc.

The polymerization is usually carried out by mixing the catalyst components in an inert diluent such as a hydrocarbon solvent, e.g., hexane, benzene, toluene, xylene, heptane, etc., and then adding the monomers into the catalyst mixture at atmospheric or superatmospheric pressures and t'emperatureswithin the range be- I tween about 50 and 180F. Usually atmospheric pressure is employed when polymerizing the monomers containing more than four carbon atoms in the molecule and elevated pressures are used for the more volatile C -C alpha-olefins. The time of reaction will depend upon, and is interrelated to, the temperature of the reaction, the choice of catalyst, and the pressure employed. In general, however, one-half to 5 hours will complete the reaction.

Usually, based upon 100 parts by weight of polymer to be produced, about l20to 100,000 parts by weight of solvent, and about 0.05 to 5 parts by weight of catalyst will be used in thepolymerization.

The hydrocarbon fuels which are treated with the polymers of this invention include those fuel oils containing 20 to 100 percent by weight of a petroleum residual fuel oil having an atmospheric boiling point above about 600FVT (F. Vapor Temperature). In general, these residual oil-containing fuels will have atmospheric boiling points above about 500FVT and will contain waxes ranging from C to C paraffins. The invention is particularly concerned with those residual oil-containing fuels having an ASTM pour point above about 50F. Specific examples of these fuels include, among others, marine diesel fuels, Bunker C fuel oil and the Numbers 4, 5 and 6 fuel oils as defined by ASTM D-396-67 and amendments thereto.

The polymers of the invention may be used alone as the sole additive, or in combination with other addi tives such as corrosion inhibitors, antioxidants, rust inhibitors, combustion improvers, and sludge dispersants and/or inhibitors, etc.

The invention will be further understood by reference to the following examples which include preferred embodiments of the invention.

DESCRIPTION OF THE PREFERREI5 EMBODIMENTS EXAMPLE I A polymer of C C alpha-olefins was prepared as follows:

Into a 500 ml. four-neck flask fitted with a mechanical stirrer, heating. mantle, thermometer, condenser and'inlet were charged under anhydrousconditions, 0.21 gram of TiCl l/3AlCl 30 millilitersof toluene as solvent and 0.4 gram of Al(n-C I-I After stirring the catalyst-solvent mixture at room temperature for about 30 minutes, the mixture was heated to about 75C. under a nitrogen blanket and 20 grams of an n-C -C alpha-olefin mixture dissolved in 180 grams of toluene was added thereto. The olefin mixture contained 32 wt. percent n-C alpha-olefin, 35 wt. percent n-C alpha-olefin, 22 wt. percent n-C alpha-olefin, 7.8 wt. percent n-cgg alpha-olefin and 3.2 wt. percent C alpha-olefins (wt. percent based on polymerizable material; 42 wt. percent inert material present). After addition of the alpha-olefin solution was completed, the reaction mixture was heated at 70 80C. for about 2 hours, whereupon 1 ml. of isopropyl alcohol was added to stop the reaction. The product mixture was then cooled to room temperature and thereafter mixed with about 5 volumes of methanol to precipitate the solid C -C alpha-olefin polymer which was then filtered off and dried for about 12 hours in an oven maintained at about C. and 120 mm. psig. The resulting polymer weighed 9 grams.

EXAMPLE 2 YA copolymer of propylene and C C alpha-olefins was prepared in the following manner:

A 150 cc.- stirred autoclave was charged under anhydrous conditions with 0.4 gram of triethyl aluminum, i.e., Al(C I-I 22 grams of xylene solvent and 0.42 gram of aluminum activated titanium trichloride, i.e., TiCl -l/3AlCl with a dry nitrogen blanket. The catalyst-solvent mixture was then stirred at 80C. for 2 hours. 82.2 grams of a normal hexane solution containing 8 wt. percent of the C -C alpha-olefin mixture described in Example 1 was then added to the stirred reactor contents. After addition of the C -C alpha-olefin solution was completed, propylene was pressured into the autoclave until the pressure .was

raised from atmospheric to 6 psig. Propylene pressure was maintained in the reactor for 2 hours at a temperature of 70 C. Then, after adding 0.9 gram of isopropanol to kill the reaction, the reactor was opened and the contents diluted with hexane and added to 4,000 ml. of methanol to precipitate the polymer product. The empty reactor was rinsed with 30 ml. of nhexane which was also added to the methanol. The precipitated product was then dried for about 12 hours in an oven maintained at 60C. and mm. pressure. The propylene/C C alpha-olefin copolymer product weighed 5.2 grams and had a number average molecular weight of 1890 as measured by Vapor Phase Osmometry (VPO).

EXAMPLE 3 A copolymer of butene-l and n-C alpha-olefin was prepared by reacting 4 grams of liquefied butene-l in a stirred glass closed reactor containing 10 grams of n-C alpha-olefin dissolved in a catalyst-solvent mixture consisting of 22.5 ml. of toluene and 90 ml. of nheptane, 0.4 gram of Al(n-C H and 0.2 grams of TiCl -l /3AlCl which catalyst-solvent mixture was prepared in accordance with the method of Example 1. The polymerization was then carried out by reacting the reactants at 70 80C. for about 4 hours. Termination of the reaction and recovery of the product was then carried out in accordance with the steps given in the above examples. The butene-l/docosene-l copolymer product weighed 7.8 grams and had a number average molecular weight of about 3350 as measured by Vapor Phase Osmometry.

EXAMPLE 4.

A number of polymers of lower alpha-olefins, higher alpha-olefms and cyclic olefins were prepared using the same general procedure as described in the above examples. In these runs, polymers prepared only from olefins containing six or more carbon atoms were made using the general process conditions set forth inExampie 1, with the exception that different olefinmonomers and amounts were employed. Similarly, polymers prepared from propylene were made using the process described in Example 2. Polymers prepared from butenel were made using the process described in Example 3. The resulting polymers were ,then tested in a North African residual fuel known as Brega residuum and having ASTM upper and lower pour points of 105 and l05F., respectively, and an initial atmospheric boiling point of 650FVT. The residual fuel-polymer blends were tested for ASTM pour depression since this is a measure of the ability of the polymer additive to improve the flow characteristics of the fuel. The results are given below in the following table.

TABLE III EVALUATION OF POLYMEIUC AUDIT IVES IN BREGA RESIDUAL FUEL ASTM Pour Point, F.

ASTM D-97. special procedure for black oils.

"Number average molecular weight of about 2760 (VPO). "(.opolymer prepared from 70 wt. ocladcccnc-l and 30 wt. '14 butene-l and having a number average molecular weight of about 9300 (VPO).

Number average molecular weight of about 2| l (VPO).

Number average molecular weight of about 7l80 (VPO). Copolymer prepared from 67 wt. docosene-l and 33 wt. butene-l and having a number average molecular weight of about 3350 (VPO).

"Copolymer prepared from 40 wt. docosene-l and 60 wt. hexenel and having a number average molecular weight of about 5530 (VPO).

Terpolymer prepared from 56 wt. docosene-l, 36 wt. hexene-l and 8 wt. methylene norbomene (MNB) and having a number average molecular weight of about 3640 (VPO).

*Copolymer prepared from 72 wt. docosene-l and 28 wt. styrene and having a number average molecular weight of about 8500 (VPO). Polymer of Example I. A Copolymer of Example 2.

"Copolymer prepared from 59 wt. of C,,C,,. alpha-olefin mixture described in Example 1 and 4l wt. of hexene-l and having a number 10 average molecular weight of about 2820 (VPO).

.Copolymer prepared from 72 wt. of C C alpha-olefin mixture described in Example I and 28 wt. styrene and having a number average molecular weight of about 8500 (VPO).

ery that the effectiveness of these C alpha-olefin polymers is significantly improved by incorporating lower alpha-olefins, such as propylene, butene-l hexene-l, etc., into the polymer molecule. For example, referring to the above Table, it is seen that polymers prepared only from C -C alpha-olefins are substantially less effective than polymers prepared from C C alpha-olefins and the C -C alpha-olefins. Similarly, copolymers of docosene-l'with lower alpha-olefins are more effective than homopolymers of docosene-l.

While not known with certainty, this unexpected improvement is believed to be due to the disrupting effect which the lower alpha-olefins have on the order of the polymer. Also, as is illustrated in the above Table, nonlinear olefins, e.g., styrene, 4-methyl-pentene-l cyclicdienes, etc., may be advantageously polymerized with the higher olefins.

It is not intended that this invention be limited to the specific examples presented by way of illustration. The scope of the invention is limited by the appended claims.

We claim: g

l. composition comprising a major proportion of apetroleum fuel boiling above about 500FVT and containing 20 to 100 wt. percent residual fuel oil, and

in the range of about 0.001 to about 2.0 wt. percent based on said fuel, of an oil-soluble flow improving copolymer comprising about 4 to. wt. percent of a lower monomer selected from the group consisting of C to C alpha-olefin and styrene, and about 50 to 96 5 wt. percent of a higher monomer which is a C to C linear alpha-olefin, said copolymer having a number average molecular weight within the range'of about 500 to l25,000,'s aid 'copolymer being prepared bypolymerization using a Ziegler-type catalyst which is a mixture of a combination of a Group IV, V or VI metal in combination with an organometallic compound of a Group I, II or III metal.

2. A composition according to claim 1 wherein said higher alpha-olefin is represented by the formula: "1C

CH CH (CI-l,), CH wherein n is a whole number ranging from about l8 to 26, and wherein said lower monomer is said C to C alpha-olefin.

3. A composition according to claim 2 wherein said copolymer comprises about 20 to 40 wt. percent of a C to C alpha-olefin and about 60 to wt. percent of C to C alpha-olefin. v

4. A composition according to claim 3 wherein said fuel consists essentially of residual fuel oil.

about 500 to 125,000 and being prepared by polymerization using a Ziegler-type catalyst which is a mixture of a combination of a Group IV, V or VI metal in combination with an organometallic compound of a Group I, II or III metal.

6. A composition according to claim 5 wherein said copolymer is a copolymer of styrene and docosene, and

said fuel consists" essentially of residual fuel oil. 

2. A composition according to claim 1 wherein said higher alpha-olefin is represented by the formula: H2C CH - CH2 -(CH2)n -CH3 wherein n is a whole number ranging from about 18 to 26, and wherein said lower monomer is said C3 to C8 alpha-olefin.
 3. A composition according to claim 2 wherein said copolymer comprises about 20 to 40 wt. percent of a C4 to C6 alpha-olefin and about 60 to 80 wt. percent of C22 to C30 alpha-olefin.
 4. A composition according to claim 3 wherein said fuel consists essentially of residual fuel oil.
 5. A composition comprising a major proportion of a petroleum fuel boiling above about 500* FVT and containing 20 to 100 wt. percent residual fuel oil, and a flow improving amount in the range of about 0.001 to about 2.0 wt. percent, based on said fuel, of an oil-soluble flow improver copolymer comprising about 20 to 40 wt. percent of styrene and about 60 to 80 wt. percent of a C22 to C30 alpha-olefin, said copolymer having a number average molecular weight in the range of about 500 to 125,000 and being prepared by polymerization using a Ziegler-type catalyst which is a mixture of a combination of a Group IV, V or VI metal in combination with an organometallic compound of a Group I, II or III metal.
 6. A composition according to claim 5 wherein said copolymer is a copolymer of styrene and docosene, and said fuel consists essentially of residual fuel oil. 